Azo dyestuffs



Patented Mar. 24, 1942 UNITED STATES PATENT OFFICE AZO DYESTUFF S Ernst Heinrich, Frankfort-on-the-Main-Fechenheim, Germany, assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application October 25, 1939, Serial No. 301,153. In Germany November 4, 1938 4 Claims.

My present invention relates to new azodyestufis, more particularly to those of the general formula:

in which formula R1 and R2 stand for radicles of the benzene series not containing a water v solubilizing group, Z for a member of the group /CH2X are Z CH2X wherein X, Y and Z have the aforesaid signification.

In order to further illustrate my invention the following examples are given, the parts being by weight and all temperatures in degrees centigrade.

Example 1 138 parts of 3-nitro-1-aminobenzene are diazotized and the diazo-solution thus obtained is combined with 160 parts f a-phenylamino-iso-butyric acid nitrile suspended in about 250 parts of concentrated hydrochloric acid and 2000 parts of water, with the addition of a sufficient quantity of sodium acetate so that the solution no longer has a mineral acid'reaction. The combination is finished in a short time. The azodyestuff formed dyes acetate silk reddish yellow shades particularly fast to light and corresponds with the formula:

When using as coupling component 180 parts of a-phenylamino-iso-butyric acid amide a dyestuif dyeing acetate silk likewise similar fast shades is obtained.

Example 2 The diazocompound of 138 parts of 4-nitro-1- amino-benzene is combined with parts of ozphenylamino-iso-butyric acid nitrile, advantageously suspended in about 250 parts of concentrated hydrochloric acid and about '2000 parts of water. The combination begins immediately and is finished after the addition of sodium acetate. The formed dyestuff of the formula:

is isolated. It dyes acetate silk clear yellowish orange shades of a good fastness to light.

When using as coupling component 174 parts of a-phenylamino-u-ethyl-propionic acid nitrile or 188 parts of a-phenylamino-a-ethyl-n-butyric acid nitrile the formed dyestuffs of the formulae:

/C Hz C H3 and /C H2 C H:

' omen:

respectively dye acetate silk similar shades of a likewise good fastness to light, whereas the dyestufis of the formulae:

/C Ha CH: CH:

and

O C Ha CH3 Oa'lN -N=N NH-C-CN respectively formed while using as coupling component 174 parts of a-(3-methylphenylamino)- isobutyric acid nitrile and 204 parts of the corresponding on (2 methoxy 5-methylphenyl) amino-compound respectively dye acetate silk clear reddish orange shades of a good fastness to light.

Example 3 The diazosolution obtained by diazotizing 172 parts of 2-chloro-4-nitro-1-aminobenzene is combined with 200 parts of a-phenylamino-isobutyric acid methylester dissolved in about 250 parts of concentrated hydrochloric acid and about 2000 parts of water. The combination begins immediately and is finished after the addition of sodium acetate. The formed dyestuff of the formula:

CH3 02X N=N- NH-C\CO 001513 I CH: 01

dyes acetate silk clear reddish orange shades of a good fastness to light.

When using as coupling component 180 parts of a-phenyl-amino-iso-butyric acid amide or 174 parts of a-(3-methyl-phenyl-amino) -isobutyric acid nitrile or 188 parts of oL-PhGIlYlfill'lil'lO-aethyl-butyric acid nitrile or 223 parts of uphenylamino-iso-butyric acid glycolester the respectively dye acetate silk likewise reddish orange shades of good 'fastness properties.

Example 4 The diazo compound of 138 parts of 3-nitrol-amino-benzene is combined with 204 parts of N oxethyl-N-phenyl a amino-isobutyric acid nitrile, which has been dissolved in about 250 parts of concentratedhydrochloric acid and 2000 parts of water. The combination is carried out in the presence of such an amount'of sodium acetate that the solution no longer has a mineral acid reaction, and is complete in a short time. The dyestufi thus obtained of the formula:

dyes acetate artificial silk reddish yellow shades of a good fastness to light.

When using as coupling component 218 parts of N oxethyl-N-(3-methylphenyl) oz aminoisobutyric acid nitrile the formed dyestuff dyes acetate silk somewhat more reddish yellow shades.

The dyestuif, obtained while using as coupling component 213 parts of N(fl-cyane'thyl) -N-phenyl-a-aminoiso-butyric acid nitrile, of the formula:

Hz-CHr-CN dyes acetate silk clear reddish yellow shades.

Example 5 The diazosolution obtained by diazotizing 138 parts of l-nitrc-l-aminobenzene is combined with 218 parts of N-oXethyl-N-(3-methylphenyl) -a-amino-isobutyric acid nitrile, dissolved in about 250 parts of concentrated hydrochloric acid and about 2000 parts of Water. The combination begins immediately and is finished after the addition of sodium acetate. The formed dyestuff of the formula:

CHr-CHz-OH is isolated. It dyes acetate silk clear yellowish red shades of good fastness to light.

When using as coupling component 204 parts of N-oXethyl-N-phenyl-a-amino-isobutyric acid nitrile a dyestuff is obtained which dyes acetate silk clear reddish orange shades.

While using as coupling component 202 parts of N-ethyl-N- (3-methylphenyl) -a-amino-lsobutyric acid nitrile or 202 parts of N-methyl-N- (2.5-dimethyl-phenyl)-a-isobutyric acid nitrile the formed dyestufis dye acetate silk somewhat more reddish orange shades.

Example 6 The diazosolution obtained by diazotizing 172 parts of 2-chloro-4-nitro-l-aminobenzene is combined with 218 parts -of N-oxethyl-N-(3- methyl-phenyl)-a-amino-isobutyric acid nitrile dissolved in about 250 parts of concentrated hydrochloric acid and about 2000 parts of water. The combination begin immediately and is finished after the addition ofsodium acetate. The formed dyestufi" dyes acetate silk clear bluish red shades of good fastness to light.

While using as coupling component 204 parts of N-oxethyl-N-phenyl-a-amino-isobutyric acid nitrile the formed dyestufi dyes acetate silk clear yellowish red shades whereas the application as coupling component of 227 parts of N-(p-cyanethyl) -N- (3-methylphenyl) -a-amino isobutyric acid nitrile or 221 parts of N-ethyl-N-phenylamino-isobutyric acid methyl-ester or 251 parts of the corresponding glycolester of the formula:

Oar-( 0 0 o ongcmon CzHs OH:

or of 192 parts of N-methyl-N-phenyl-a-amlno isobutyric acid amide yields dyestufis dyeing acetate silk reddish orangeshades.

Example 7 Example 8 The dyestuff of the formula:

Hr-CHgOII /CH: OnN-QN=N-D- CN CHa NO: C I

omomon obtained by combinin the diazocompound of 183 parts of 2.4-dinitro-l-amino-benzene with 218 parts of N-oxethyl-N-(S-methylphenyl)-a-amino-isobutyric acid nitrile dyes acetate silk clear reddish violet shades of good fastnes properties.

I claim: 1. Azodyestuff of the general formula:

in which formula R1 and R: stand for radicles of the benzene series not containing a water soluhilizing group, Z for a member of the group consisting of hydrogen, alkyl, hydroxyalkyl and cyanalkyl, X for a member of the group consisting of hydrogen and methyl, Y for a member of the group consisting of CN, CONI-Iz and COORa, R3 standing for a member of the group consisting of alkyl and hydroxyalkyl, which dyestufis dye cellulose esters and ethers, particularly acetate silk mostly bright shades of a remarkable iastness, particularly to light.

2. The azodyestufi of the formula:

which dyestuff dyes acetate silk clear reddish orange shades of a good fastness to light.

3. The azodyestufi of the formula:

/CH2CH$ CHaCH: G1

which dyestufi dyes acetate silk reddish orange shades of good fastness properties.

4. The azodyestufi of the formula:

CH: C!

which dyestufi dyes acetate silk reddish orange shades of good fastness properties.

ERNST HEINRICH. 

